The present study is primarily designed to develop an environmentally-benign approach for the recovery of precious metals, especially gold, from the ever increasingly-discarded electronic wastes (e-waste). By coupling the metal reduction process with an increase in the intrinsic oxidation state of the aniline polymers, and the subsequent re-protonation and reduction of the intrinsically oxidized polymer to the protonated emeraldine (EM) salt, polyaniline (PANi) films and polyaniline coated cotton fibers are able to recover metallic gold from acid/halide leaching solutions of electronic wastes spontaneously and sustainably. The current technique, which does not require the use of extensive extracting reagents or extal energy input, can recover as much as 90%of gold from the leaching acidic solutions. The regeneration of polyaniline after gold recovery, as confirmed by the X-ray photoelectron spectroscopy measurements, promises the continuous operation using the current approach. The as-recovered elemental gold can be further concentrated and purified by incineration in air.